Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

Cu、Sn、Ag同位素在古金属制品溯源研究中的应用

近年来,随着同位素分析方法的不断突破和新一代多接收电感耦合等离子体质谱(MC-ICP-MS)测试技术的广泛应用,Cu、Sn、Ag等非传统同位素在古代金属制品溯源研究中显示出较好的应用前景。本文综述了近20年来Cu、Sn、Ag同位素在古代金属制品应用研究的相关进展,并展望了其应用前景:①由于不同矿床之间Cu、Sn、Ag同位素存较大重叠,这些同位素均难以作为独立的证据追溯金属制品的地质来源;②Cu同位素在原生矿石与表生矿石之间存在较大的分馏,是示踪铜矿石类型的可靠方法,Ag同位素也具推断银矿石类型的潜力;③将Cu、Sn、Ag同位素与Pb同位素、微量元素相结合,并采用合理的统计方法,开展综合溯源研究将是今后应用非传统同位素进行古代金属制品溯源研究的发展方向。

滇西保山地块金厂河Fe-Cu-Pb-Zn矽卡岩型多金属矿床黑柱石成因及地质意义

黑柱石是一种矽卡岩型铅锌及铁矿床中少见的矿物,与铅锌矿体、磁铁矿体关系密切。为查明黑柱石成矿过程中与铅锌铁铜多金属成矿作用的关系,本文对金厂河Fe-Cu-Pb-Zn多金属矿床中的黑柱石产状、矿物共生组合、化学成分、分带性等开展了研究。根据电子探针数据计算可得,金厂河矿区黑柱石的化学式为:Ca_(0.95-1.08)(Fe_(0.87-1.97)Mn_(0.08-0.36)Mg_(0.01-0.06))^(2+)_((1.89-2.03))(Fe_(0.82-1.04)Al_(0.01-0.03))^(3+)_((0.88-1.15))[Si_(1.94-2.08)O_(7)]O(OH)。结合矿物组合类型、产状、分带特征等,推测矿床内矽卡岩由内带逐渐向外带交代的趋势。金厂河矿区主要有3种矿物共生组合:黑柱石+磁铁矿组合,黑柱石+磁铁矿+黄铁矿+黄铜矿组合,黑柱石+方铅矿+闪锌矿+黄铜矿组合,分别对应三个不同的蚀变阶段:晚期矽卡岩阶段(代表组合Ⅰ),以石榴子石的分解为主,形成大量的黑柱石;退蚀变阶段(代表组合Ⅱ),以阳起石、黄铜矿、黄铁矿发育为主;石英-硫化物阶段(代表组合Ⅲ),以发育大量的方铅矿、闪锌矿为主,同时这一阶段内黑柱石分解,形成阳起石、方解石、磁铁矿等。此外,黑柱石的稀土元素配分模式与石榴子石的类似,一定程度上保留了石榴子石的稀土元素特征。研究认为:黑柱石是早期石榴子石退化分解的产物,矿床自内向外逐渐交代,形成了铅锌铜矿体中以锰质黑柱石为主,而磁铁矿体、铜矿体中以含锰黑柱石为主的分带特性。锰质黑柱石有利于铅锌矿的形成,而对于磁铁矿有贫化的影响,同时也可为矿区揭露中酸性岩体和深部找矿提供重要科学意义。

Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions

In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.

Cu(II)在对甲苯磺酸铜+DMSO中的电还原

制备了对甲苯磺酸铜并首次用于电化学实验.差示扫描量热和热重曲线测定表明,对甲苯磺酸铜结晶容易脱除全部结晶水,无水盐在空气中不潮解.用循环伏安曲线、计时电流曲线和恒电流电解后的电位-时间曲线研究Cu(Ⅱ)在二甲基亚砜(DMSO)溶液中的电还原.结果表明,Cu(II)电还原为Cu的反应分两步进行,其中第一步是可逆过程.测定了Cu(II)在DMSO溶液中的扩散系数.

泉州湾滩涂沉积物对Cu(II)的吸附实验

研究了Cu(II) 在泉州湾滩涂沉积物上的吸附行为。探讨了pH和温度对吸附作用的影响,测定了其吸附等温线。实验结果表明,常温下Cu(II) 在泉州湾滩涂沉积物上的吸附平衡时间约需3.5 小时;吸附量随pH的升高先增大而后减少,pH=6.0左右时达最大;吸附量随温度的升高而增大;其吸附行为可以很好地用Langmuir型吸附等温线来描述。并在此基础上初步探讨了Cu(II)在泉州湾滩涂沉积物上的吸附机理。

Trace Element Geochemistry of Magnetite from the Fe(-Cu) Deposits in the Hami Region, Eastern Tianshan Orogenic Belt, NW China

Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite： Ni–Mn–V–Ti（Factor 1）, Mg–Al–Zn（Factor 2）, and Ga– Co（Factor 3） magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe（–Cu） deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe（–Cu） deposits may be related to felsic magmatism.

Electrochemical behavior of Cu(II) reduced in CH3OH and DMSO

The cyclic voltammetry and the potential-time curve after galvanostaticelectrolysis were used to study the electrode processes of Cu(II) in CH_3OH solution and DMSOsolution. The electroreduction of Cu(II) to Cu on a Pt electrode proceeds in two steps: Cu(II) + evelence Cu(I); Cu(I) + e velence Cu. The reduction potential of Cu(II) in DMSO solution is morenegative than that in CH_3OH solution, and the diffusion coefficient of Cu(II) ion in DMSO solutionis larger than that in CH_3OH solution because the polarity of DMSO is larger than that of CH_3OHobservably and has a stronger solvating power.

Adsorption of Cu(II) on maghnite from aqueous solution: Effects of pH, initial concentration, interaction time and temperature

The adsorption behaviour of Cu2+ onto maghnite was conducted under batch conditions. The effect of time, pH of the dispersion, temperature and initial metal concentration on the adsorption of Cu2+ onto maghnite was investigated. In this study, 94% of Cu(II), was adsorbed on the maghnite clay when the equilibrium was reached at 120 min. The adsorption of Cu2+ was a fast process that followed the pseudo-second-order kinetics. This process could be described by the Langmuir model and gave a maximum Cu2+ adsorption capacity of 21.78 mg/g at 293 K. The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnKd vs. 1/T plots. The adsorption was endothermic reaction. The adsorption process for this natural maghnite is more spontaneous because the values of ΔG are less negative. The results suggested that natural maghnite was suitable as sorbent material for the recovery and adsorption of metal ion from aqueous solutions.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex with Tridentate Schiff Base and Azido Bridge

A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.

Synthesis,Structure and Properties of a Novel Copper(Ⅱ)-2,2'- biimidazole Complex-supported Compound:[Cu(H_2biim)_2]{[Cu(H_2biim)_2 ]_2[H_(10)W_(12)O_(44)]}·8H_2O

A new copper（II）-2,2＇-biimidazole metal-organic POMs-supported compound [Cu（H2biim）2]{[Cu（H2biim）212[H10W12O44]}＇8H2O （H2biim = 2,2＇-biimidazole） has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800（2）, b = 13.437（3）, c = 13.685（3） A, V = 1922.5（7） A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F（000） = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections （I 〉 2σ（I））. X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu（H2biim）2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.＇-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.

Atomic Absorption and Vibrational Spectral Magnetic Studies on the Removal of Cu(II) and Co(II) Ions Using Synthetic Nano Adsorbent Fe₃O₄

Adsorption of Cu(II) and Co(II) from aqueous solutions on synthetic nano Fe3O4 has been studied. The effect of experimental parameters such as initial concentration of the metal ions, adsorbent dosage, contact time and pH has been investigated. Optimum removal efficiency of Cu(II) ion was found to be 97.8% with the dose rate of 1.07 g/L in 60 minutes at pH = 5.5 and for Co(II) ion, it was found to be 99.2% with the dose rate of2.57 g/L in 10 minutes at pH = 5.4. The removal of Co(II) ions require only 10 minutes with the efficient removal of 99.2%, whereas Cu(II) ions require 60 minutes with the maximum removal of 97.8%. In order to understand the effective removal of Cu(II) and Co(II) ions on Fe3O4, room temperature magnetic measurement was carried out using Vibrational Spectrum Magnetometer (VSM), before and after adsorption with a maximum applied magnetic field of 20,000 G.

Biosorption of Cu(II) Ions from Aqueous Solution by Red Alga (<i>Palmaria Palmata</i>) and Beer Draff

In this study, the ability of red alga (Palmaria palmata) and beer draff (brewery waste) for Cu(II) removal was investigated. The influence of factors, such as pH, initial copper concentrations, and contact time, were also studied. Results showed the adsorption process was strongly dependent on the pH value and initial concentration. The optimum pH value was in the range of 5-6. The Langmuir isotherm model performed better than other models, suggesting monolayer adsorption prevailed in the adsorption process. The theoretical adsorption capacities for Cu(II) were 12.7 mg/g and 9.01 mg/g for red alga and beer draff, respectively. The spectroscopy analyses and desorption studies showed that chemical bonding was the main mechanism in the adsorption process rather than ion exchange. The functional groups of amino, hydroxyl, carboxyl, phenolic hydroxyl, sulphonic group and C–O, –NH stretch might be involved in adsorption. After adsorption, both materials were successfully regenerated by nitric acid at a concentration of 10 mmol/L. Furthermore, the phenomenon that only 7% of adsorbed Cu(II) on red alga and 11% on beer draff were desorbed by sodium chloride solution suggested potential alternative of both materials for the treatment of road runoff containing considerable amounts of de-icing salt.

Comparative Studies of Some Novel Cu(II) Polymeric Complexes Derived from Cyanoacetylhydrazine (CAH;L). The Role of Solvents Used on the Structure and Geometry of the Isolated Cu²⁺Complexes

Novel polymeric Cu2+ complexes derived from the reaction of cyanoacetylhydrazine (CAH;L) with CuCl2•2H2O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, 1H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that CAH behaves in different ways towards the coordination of the Cu2+ ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu2+ ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu2+ complexes. EPR studies indicate the existence of polymeric complexes depending on the results of g-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.

不同温度下制备的椰壳生物炭对水中Cu(II)的吸附研究

化工业的快速兴起,使含有农药、油漆以及化肥等有害废水和废渣大量排放,导致环境中的铜污染进一步恶化。因此,要降低和消除环境中过量的金属铜,吸附是一种行之有效的技术手段。生物炭因其制备费用低,吸附性能好以及对环境友好等特点而被广泛研究使用。本实验以我国海南省来源广泛的椰壳作为原材料,分别在500℃、600℃和700℃条件下制备生物炭(分别记为T500、T600和T700)。利用三种温度制备的椰壳生物炭研究不同初始浓度、生物炭投加量、溶液初始pH值以及吸附时间等因素对水中Cu(II)的吸附特征。研究结论如下:1) 三种温度下制备的椰壳生物炭对水中Cu(II)都具有较好的吸附效果,在相同条件下,三种生物炭的吸附能力:T700 】T600 】T500。2) 在水中Cu(II)初始浓度为60 mg/L,投加量为0.2 g,pH为4,吸附时间为3 h时,T700的最大吸附量达到8.6833 mg/g。

Geochemical studies on REE and trace elements from several Cu-Au deposits along the lower Yangtze metallogenic valley, central-southern Anhui Province

The Yangtze Valley was one of the most important metallogenic regions during the Jurassic-Cretaceous period in East China, where more than 200 polymetallic Cu-Fe-Au, Mo, Zn, Pb, Ag deposits have been found. Trace elements were chemically analyzed and the relevant data were collected from literature for the Yanshanian (Mesozoic) igneous rocks which have close relationship with Cu-Au mineralization. Copper mineralization in the lower Yangtze Valley can be divided into three major types: skarn type, porphyry type and volcanic type. The porphyry type is of rare occurrence, such as the Shaxi porphyry copper deposit in the northern part of the lower Yangtze metallogenic valley. This paper focuses on the REE and trace element geochemistry of several Cu-Au deposits along the lower part of Yangtze metallogenic valley in Anhui. The results showed that there are differences in REE distribution for these four types of Cu-Au mineralization, which confine the sources of REE and trace elements as well as other mantle and transitional compatible elements. The results of both REE and trace element geochemical studies showed that these elements with different characteristics have different origins, probably representing different sources of Cu-Au deposits in the deep crust and upper mantle environments. The 40Ar/39Ar dating of one biotite sample gave an age of 131 Ma with a high level of confidence, which represents the age of formation of the Shaxi porphyrite intrusive with porphrytic Cu-Au mineralization, which is consistent with that of the majority of the adjacent acid intrusives with mass Cu-Au mineralization along the Yangtze metallogenic belt in the Yanshanian period (Mesozoic). This is the first attempt to use the high precision method to date the Shaxi porphyrite intrusive.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex [Cu(C_(12)H_(17)N_2O)(NCS)]_2 with Tridentate Schiff Base Ligand N-(Salicylidene)-3-dimethylaminopropylamine

A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.

SYNTHEIS, SITUCTURE AND CHARACTERIZATION OF BINUCLEAR Cu(II)COMPLEX[Cu(C_6H_5COO)_2(C_5H_6N_2)]_2.(C_4 H_8O)_2

At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (C5 H5 COO)2(C5 H5 N2)]2. (C4 H5 O)2. The structure of the complex was characterized by elemental analyses. IR spectra, TG-DTA. The structure of the compound has been solved by direct method and Fourier synthesis, and refined by block-diagonal and full matrix least-squares method to a final R of 0.04329 for 3671 independent reflection of I>e(I). The crystals are triclinic, C46H45N4O10Cu2.Z=1, Mr=943.93, space group P-1, with cell parameters, a=10.806(1); b=11.169(3);c=11.729(2)A; α=71.99(2),β=89.38(1)°; γ=81.37(1); V=1330.1A3; Dc=1.172g.cm-3;μ=8.5cm-1. The copper(II) ion is coordinated by four bridging bidentate benzoate and two 2-aminopyridine to form dimeric molecules.

离子印迹磁性碳纳米球基电化学传感器用于铜(II)的选择性检测

本文报道一种基于Cu(II)离子印迹聚合物为识别元件的电化学传感器。通过耦合表面离子印迹和电化学沉积的制备方法,制备了由磁性碳纳米球组成的离子印迹聚合物电极。所组装的传感器表现出对Cu(II)检测的特异识别性和高灵敏特性。通过场发射扫描电子显微镜和透射电子显微镜对印迹聚合物的微观形貌进行表征,采用傅里叶变换红外光谱对其官能团和化学结构进行表征。传感器电化学性能表明,与非印迹电极和裸电极相比,印迹电极对Cu(II)具有更强的选择性和更高的灵敏度。传感器对浓度为10^(-6)至10^(-10) mol L^(-1)的Cu(II)表现出良好的线性相应电流,其检测限提升至5.138×10^(-16) mol L^(-1)(S/N=3)。此外,该传感器具有良好的抗干扰性、重现性和稳定性,为金属离子的检测提供了新的策略。

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.